EP2099082B1 - Matériau piézocéramique, élément piézoélectrique et détecteur de cliquetis sans résonance - Google Patents

Matériau piézocéramique, élément piézoélectrique et détecteur de cliquetis sans résonance Download PDF

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EP2099082B1
EP2099082B1 EP09003122.0A EP09003122A EP2099082B1 EP 2099082 B1 EP2099082 B1 EP 2099082B1 EP 09003122 A EP09003122 A EP 09003122A EP 2099082 B1 EP2099082 B1 EP 2099082B1
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Prior art keywords
piezoelectric
piezoceramic material
piezoelectric element
piezoceramic
sensor
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EP2099082A2 (fr
EP2099082A3 (fr
Inventor
Masato Yamazaki
Hideaki Hiramitsu
Manabu Horiguchi
Yukihiro Hamaguchi
Katsuya Yamagiwa
Takeshi Mitsuoka
Kazushige Ohbayashi
Ryotaro Tawara
Tomohiro Hirata
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Niterra Co Ltd
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NGK Spark Plug Co Ltd
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Priority claimed from JP2008185029A external-priority patent/JP5062759B2/ja
Priority claimed from JP2008317858A external-priority patent/JP5222120B2/ja
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Publication of EP2099082A2 publication Critical patent/EP2099082A2/fr
Publication of EP2099082A3 publication Critical patent/EP2099082A3/fr
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
    • C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/6262—Milling of calcined, sintered clinker or ceramics
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L23/00—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid
    • G01L23/22—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid for detecting or indicating knocks in internal-combustion engines; Units comprising pressure-sensitive members combined with ignitors for firing internal-combustion engines
    • G01L23/221—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid for detecting or indicating knocks in internal-combustion engines; Units comprising pressure-sensitive members combined with ignitors for firing internal-combustion engines for detecting or indicating knocks in internal combustion engines
    • G01L23/222—Devices or apparatus for measuring or indicating or recording rapid changes, such as oscillations, in the pressure of steam, gas, or liquid; Indicators for determining work or energy of steam, internal-combustion, or other fluid-pressure engines from the condition of the working fluid for detecting or indicating knocks in internal-combustion engines; Units comprising pressure-sensitive members combined with ignitors for firing internal-combustion engines for detecting or indicating knocks in internal combustion engines using piezoelectric devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/093—Forming inorganic materials
    • H10N30/097—Forming inorganic materials by sintering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/30—Piezoelectric or electrostrictive devices with mechanical input and electrical output, e.g. functioning as generators or sensors
    • H10N30/302—Sensors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8548—Lead-based oxides
    • H10N30/8554—Lead-zirconium titanate [PZT] based
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
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    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/785—Submicron sized grains, i.e. from 0,1 to 1 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the present invention relates to a piezoceramic material suitable for use in piezoelectric sensors such as pressure sensor, acceleration sensor, knock sensor, yaw rate sensor, gyro sensor and shock sensor and other piezoelectric devices, a piezoelectric element using the piezoceramic material and a non-resonance knock sensor using the piezoelectric element.
  • Each of the piezoelectric sensors includes a piezoelectric element equipped with a sintered piezoceramic body (bulk) and at least one pair of element electrodes so as to convert a mechanical stress applied thereto to an electricity or voltage by the piezoelectric effect of the piezoceramic body and generate an electrical signal based on the converted electricity or voltage.
  • the sensitivity (output voltage) of the piezoelectric sensor varies as the piezoelectric characteristics of the piezoceramic body change with the ambient temperature of the operating environment.
  • the piezoelectric sensor When the temperature of the piezoelectric sensor changes during operation or changes with the ambient temperature of the operating environment, there occurs a thermal stress in the piezoelectric element due to the difference in thermal expansion between the piezoceramic body and the element electrodes or other adjacent sensor parts. There also occurs a voltage in the piezoelectric sensor by the pyroelectric effect of the piezoceramic body in response to the temperature change. These introduce noise into the output of the piezoelectric sensor and thus lead to variations in the sensitivity of the piezoelectric sensor. Further, the piezoelectric characteristics of the piezoceramic body may deteriorate to cause a decrease in sensor output under the weight applied to the piezoelectric element.
  • the operating temperature of the piezoelectric sensor is generally set to about -40°C to 170°C. It is however desired that the piezoelectric element exhibit no variations in temperature characteristics over a wider temperature range in view of the fact that the piezoelectric sensors are used under severe conditions in e.g. automotive engines.
  • Japanese Patent No. 2789374 discloses PZT (lead zirconate titanate) piezoceramic materials doped with Sn, Nb and Sb so as to obtain improvements in thermal stability by the addition of Sn and to enable low-temperature sintering and softening (i.e. improvements in piezoelectric characteristics with large crystal distortion) by the addition of Nb and Sb.
  • PZT lead zirconate titanate
  • the above conventional piezoceramic materials need further improvements in piezoelectric and temperature characteristics.
  • piezoceramic materials having a piezoelectric constant d33 of 340 pC/N or larger (as an index of piezoelectric sensitivity) and piezoceramic materials having a Curie point of 340°C or higher (as an index of heat resistance) so that the piezoceramic materials can suitably be applied to the piezoelectric sensors in the automotive engines, which could reach a maximum temperature of about 170°C.
  • no reports have been made on any piezoceramic materials having a piezoelectric constant d33 of 340 pC/N or larger and/or a Curie temperature of 340°C or higher.
  • a piezoceramic material having a composition represented by Pb m ⁇ Zr 1-x-y-z Ti x Sn y (Sb 1-n Nb n ) z ⁇ O 3 where 1.000 ⁇ m ⁇ 1.075, 0.470 ⁇ x ⁇ 0.490, 0.020 ⁇ y ⁇ 0.040, 0 ⁇ n ⁇ 1.000 and 0 ⁇ z ⁇ 0.025 and a crystallite size of 30 to 39 nm.
  • a piezoceramic material having a composition represented by Pb m ⁇ Zr 1-x-y-z Ti x Sn y (Sb 1-n Nb n ) z ⁇ O 3 where 1.000 ⁇ m ⁇ 1.075, 0.470 ⁇ x ⁇ 0.490, 0.020 ⁇ y ⁇ 0.040, 0 ⁇ n ⁇ 1.000 and 0 ⁇ z ⁇ 0.025 and a piezoelectric constant d33 of 340 pC/N or larger.
  • a piezoelectric element comprising an element body formed of the above piezoceramic material.
  • a non-resonance knock sensor comprising: a piezoelectric element having an element body formed of the above piezoceramic material and at least one pair of electrodes arranged on the element body; a support member having a support portion to support the piezoelectric element; a weighting member disposed on the piezoelectric element to press the piezoelectric element against the support portion; and a resin molded part covering the piezoelectric element and the weighting member from the outside of the support member.
  • a non-resonance knock sensor comprising: a piezoelectric element having an element body formed of the above piezoceramic material and a pair of first and second electrodes arranged on the element body; a support member having a support portion to support the piezoelectric element; and a weighting member disposed on the piezoelectric element to press the piezoelectric element against the support portion, wherein at least part of a surface of the first electrode faces a bottom surface of the weighting member when the piezoelectric element and the weighting member are projected in a thickness direction of the piezoelectric element; and the ratio of an area of said at least part of the surface of the first electrode to an area of the bottom surface of the weighting member is 45% or higher.
  • a piezoceramic material according to one exemplary embodiment of the present invention (hereinafter just referred to as “piezoceramic material”) is PZT (PbTiO 3 -PbZrO 3 ) ceramic doped with Sn, Sb and Nb.
  • the piezoceramic material has a composition represented by Pb m ⁇ Zr 1-x-y-z Ti x Sn y (Sb 1-n Nb n ) z ⁇ O 3 where 1.000 ⁇ m ⁇ 1.075, 0.470 ⁇ x ⁇ 0.490, 0.020 ⁇ y ⁇ 0.040, 0 ⁇ n ⁇ 1.000 and 0 ⁇ z ⁇ 0.025, so as to differ in composition from the morphotoropic phase boundary, benefit from the substitution (doping) effect of Sn, Sb and Nb and thereby secure compatibility between the piezoelectric characteristics and temperature stability of capacitance Cp in the present embodiment.
  • the piezoceramic material attains a piezoelectric constant d33 of 340 pC/N or larger.
  • the piezoelectric constant d33 is defined as the amount of electric charges generated by the positive piezoelectric effect of the piezoceramic material under the application of a mechanical force, stress, pressure etc. thereto. It is said that, the larger the piezoelectric constant d33, the larger the amount of electric charges generated by the piezoceramic material and, in the case of using the piezoceramic material in a piezoelectric sensor, the higher the output (sensitivity) of the piezoelectric sensor.
  • the piezoceramic material decreases in piezoelectric constant d33 due to the difference from the PZT composition. If m > 1.075, the piezoceramic material decreases in piezoelectric constant d33 due to the formation of PbO. If x ⁇ 0.470, the amount of Ti in the piezoceramic material is so small that the piezoceramic material may have a large capacitance change rate of ⁇ Cp > 2500 ppm/K. If 0.490 ⁇ x, the piezoceramic material tends to be low in piezoelectric constant d33 and shows a large deterioration of the piezoelectric constant d33 by heat.
  • the piezoceramic material has a crystallite size of 30 to 39 nm.
  • the crystallite is defined as a domain (microcrystal) that can be regarded as a single crystal, and the crystallite size is used as a parameter of crystallinity (crystalline perfection) and defined as the size of that domain.
  • Most materials are made of a plurality of crystallites. If the crystallite size is less than 30 nm, the domains in which all parts have the same crystallographic orientation are small. This makes it difficult to improve the piezoelectric characteristics of the piezoceramic material.
  • the piezoelectric characteristics of the piezoceramic material can be improved by raising the sintering (firing) temperature of the piezoceramic material and thereby increasing the crystallite size of the piezoceramic material.
  • the composition of the piezoceramic material breaks down by evaporation of the volatile elements Pb, Sn and Sb so that the piezoelectric characteristics of the piezoceramic material would be deteriorated rather than improved when the sintering temperature of the piezoceramic material becomes too high. It is conceivable to control the crystallite size by adjusting not only the sintering temperature but the calcination conditions and raw powder pulverized size of the piezoceramic material as appropriate.
  • the crystal grain size of the piezoceramic material it is difficult to improve the piezoelectric characteristics of the piezoceramic material by controlling the crystal grain size of the piezoceramic material as the crystal grain size does not always reflect the above-explained crystallite domain size of the piezoceramic material. If the crystal grain size is too large, however, there is a tendency that the spaces between crystal grains of the piezoceramic material become increased to decrease the amount of electric charges generated by the application of a mechanical load to the piezoceramic material. The crystallite size, rather than the crystal grain size, is thus used as a control parameter for improving the piezoelectric characteristics of the piezoceramic material in the present embodiment.
  • XRD X-ray diffraction
  • the piezoceramic material has a Curie temperture Tc of 340°C or higher.
  • the heat resistance of the piezoceramic material increases with Curie temperature Tc so that the piezoceramic material becomes more suitable for high-temperature uses such as automotive engine.
  • the pie formaramic material also preferably has a capacitance change rate ⁇ Cp of 2500 ppm/K or lower in a temperature range of 20°C to 150°C.
  • the amount of change of the capacitance Cp with temperature becomes small as the capacitance change rate ⁇ Cp decrease.
  • a low capacitance change rate ⁇ Cp leads to a reduction in the sensitivity variations of the piezoelectric sensor.
  • the rate of deterioration of the piezoelectric constant d33 (hereinafter just referred to as "piezoelectric constant deterioration rate ⁇ d33") of the piezoceramic material during heat-resistance test for 10 hours at 250°C in the air falls within -10%.
  • the piezoelectric constant deterioration rate ⁇ d33 is given by the expression ⁇ (piezoelectric constant d33 after heat-resistance test) - (initial piezoelectric constant d33) ⁇ / (initial piezoelectric constant d33).
  • the heat resistance of the piezoceramic material increases as the piezoelectric constant deterioration rate ⁇ d33 decreases in absolute value.
  • the pie formaramic material can be favorably applied to a piezoelectric element by arranging at least at least one pair of positive and negative element electrodes on the piezoceramic material. Since the piezoceramic material has good stability, heat resistance and durability as described above, the thus-obtained piezoelectric element is suitable for use in a piezoelectric sensor such as combustion pressure sensor, knock sensor, gyro sensor etc., a piezoelectric resonator, a piezoelectric vibrator, a piezoelectric actuator, an ultrasonic motor, a fingerprint identification device or a pressure-sensitive device.
  • a piezoelectric sensor such as combustion pressure sensor, knock sensor, gyro sensor etc.
  • a piezoelectric resonator such as combustion pressure sensor, knock sensor, gyro sensor etc.
  • a piezoelectric vibrator such as a piezoelectric vibrator
  • a piezoelectric actuator such as ultrasonic motor, a fingerprint identification device or a pressure
  • the piezoceramic material and the piezoelectric element can be produced by the following procedures.
  • oxide, carbonate or bicarbonate raw powders are weighed out and blended together to attain the above-specific piezoceramic material composition.
  • the powder blend is added to a dispersion medium such as ethanol or water, wet-blended and pulverized by a ball mill etc.
  • the resulting slurry is dried to yield a mixed raw powder material.
  • the raw powder material is calcinated e.g. in the air at 600 to 1100°C for 10 to 300 minutes.
  • the calcinated powder material is mixed with an organic binder such as polyvinyl alcohol or polyvinyl butyral, a water-soluble binder and a dispersion medium such as alcohol, ether or water and wet-pulverized by a ball mill etc.
  • the resulting slurry is dried to yield a pulverized powder material.
  • the pulverized powder material is compacted into a desired shape.
  • the compact can be of any appropriate shape such as ring shape or disc shape.
  • CIP cold isostatic pressing
  • the compact is sintered e.g. at 900 to 1250°C for 1 to 10 hours.
  • At least one pair of element electrodes are formed on opposite sides of the sintered compact by, e.g., in the case where the sintered compact is of disc shape, surface grinding the opposite disc surfaces of the sintered compact, applying a conductive paste to the ground opposite surfaces of the sintered compact by screen printing and baking the conductive paste as appropriate.
  • the conductive paste is generally prepared from a conductive component, a glass frit and an organic medium.
  • the conductive component are powders of noble metals such as silver, gold, palladium and platinum and alloys thereof and any mixture thereof.
  • the conductive component there can also be used powders of other metals such as copper and nickel and alloys thereof and any mixture thereof.
  • the glass frit are those containing SiO 2 , Al 2 O 3 , ZnO and TiO 2 .
  • the organic medium are those commonly used for this kind of conductive paste, such as alcohol and ether.
  • the sintered compact is polarized through the application of a direct-current voltage of about 3 to 20 kV/mm between the electrodes for about 10 to 100 minutes in an insulating oil such as silicone oil in a temperature range of room temperature to about 200°C.
  • the polarization may alternatively be conducted by applying a high voltage to the sintered compact while overheating the sintered compact in the air.
  • the electrodes may optionally be removed.
  • the thus-obtained sintered compact with or without the element electrodes can be used as the piezoceramic material.
  • the piezoelectric element 15 of a non-resonance knock sensor 10 is as a piezoelectric element 15 of a non-resonance knock sensor 10 as shown in FIG. 5 .
  • the knock sensor 10 is designed as a so-called "center-hole type" non-resonance knock sensor for an internal combustion engine that is short cylindrical in shape as a whole with a sensor mount hole 12f formed in the center thereof for mounting on a cylinder block of the engine.
  • the knock sensor 10 includes a resin molded part 11 and a sensor unit 20 in which the piezoelectric element 15 is built together with a support member (metal shell) 12 and a weighting member 17 as shown in FIGS. 5 and 6 .
  • the piezoelectric element 15 has an annular element body 15c formed of the piezoceramic material and a pair of element electrodes 15a and 15b formed on upper and lower sides of the element body 15c.
  • the support member 12 has a cylindrical portion 12a formed with an external thread 12x and a flanged support portion 12b formed on a lower end of the cylindrical portion 12a to support thereon the piezoelectric element 15.
  • the weighting member 17 has an annular shape and is fitted around the cylindrical portion 12a and disposed on the piezoelectric element 15 to press the piezoelectric element 15 against the support portion 12b.
  • the resin molded part 11 has a casing portion 11 a disposed around the sensor unit 20 to cover the piezoelectric element 15 and the weighting member 17 etc. from the outside of the support member 12 and a connector portion 11b radially outwardly protruding from an outer circumferential surface of the casing portion 11a.
  • the sensor unit 20 further includes insulating members such as a cylindrical insulating sleeve 13s and annular insulating plates 13p and 13t, upper and lower annular lead electrodes 16 and 14 and holding members such as a disc spring 18 and a nut 19 as shown in FIGS. 5 and 6 .
  • insulating members such as a cylindrical insulating sleeve 13s and annular insulating plates 13p and 13t, upper and lower annular lead electrodes 16 and 14 and holding members such as a disc spring 18 and a nut 19 as shown in FIGS. 5 and 6 .
  • the lead electrodes 16 and 14 are arranged on and connected to the element electrodes 15a and 15b, respectively.
  • Flake-shaped terminal portions 16a and 14a are formed on the lead electrodes 16 and 14 and passed through the connector portion 11b for connection to an external connector. (In FIG. 5 , only the terminal portion 14a is illustrated for simplicity.)
  • the insulating plate 13p is interposed between the support portion 12b and the lower lead electrode 14, whereas the insulating plate 13t is interposed between the upper lead electrode 16 and the weighting member 17.
  • the insulating sleeve 13s is fitted around the cylindrical portion 12a.
  • the disc spring 18 is fitted around the cylindrical portion 12a and placed on the weighting member 17.
  • the nut 19 is formed with an internal thread 19y and screwed onto the external thread 12x so as to hold the insulating plate 13p, the lower lead electrode 14, the piezoelectric element 15, the upper lead electrode 16, the insulating plate 13t, the weighting member 17 and the disc spring 18 (in order of mention) between the support portion 12b and the nut 19 and thereby allows the weighting member 17.
  • the piezoelectric element 15 is placed under mechanical load (preset load) in an assembled state of the knock sensor 10.
  • the piezoelectric element 15 may be held in position under mechanical load by an adhesive member or mold.
  • the piezoelectric element 15 When a mechanical force, stress, pressure etc. is applied to the piezoelectric element 15 in this sensor state, the piezoelectric element 15 generates an electricity or voltage by its positive piezoelectric effect. The generated electricity or voltage is taken out of the piezoelectric element 15 through the lead electrodes 14 and 16.
  • the knock sensor 10 further includes an electric circuit to take the electricity or voltage from the piezoelectric element 15 and convert the electricity or voltage into an electrical signal (voltage signal).
  • the electric circuit may be integrated into or arranged separately on the knock sensor 10.
  • the whole of the element electrode 15a vertically faces the weighting member 17 through the insulating plate13t.
  • the ratio of the area S2 of the at least part of the upper surface SB of the element electrode 15a to the area S 1 of the lower surface SA of the weighting member 17 is 45% or higher.
  • the upper surface area S2 of the element electrode 15a is smaller than the lower surface area S 1 of the weighting member 17, it is possible to decrease the amount of electrode material used in the element electrode 15a and the amount of electrode material used in the counter electrode 15b and thereby reduce the cost of the knock sensor 10. It is also possible to secure a higher degree of flexibility in changing the surface area ratio S2/S1 and adjust the capacitance Cp of the piezoelectric element 15 as appropriate. If the upper surface area S2 of the element electrode 15a is too much smaller than the lower surface area S 1 of the weighting member 17, however, the sensitivity of the knock sensor 10 becomes deteriorated due to lowered sensor output.
  • these chamfered regions 15f are not included in the top surface SB of the element electrode 15a. Any surface region, other than the chamfered regions 15f, of the element electrode 15a vertically facing the weighting member 17 is regarded as the top surface SB of the element electrode 15a.
  • Piezoceramic materials of Examples 1 to 9 and Comparative Example 1 to 6 were produced as follows. In each of Examples 1 to 9 and Comparative Examples 1 to 6, raw powders of zirconium oxide, titanium oxide, tin oxide, antimony oxide and niobium oxide were weighed out and blended together to form a composition of TABLE 1 when sintered. The resulting powder blend was added to ethanol, subjected to wet-blending/pulverization by a ball mill and dried to yield a mixed raw powder material. The raw powder material was calcinated in the air at 800°C for 2 to 3 hours. The pulverized size of the calcinated powder material was about 0.6 to 1 ⁇ m.
  • the calcinated powder material was mixed with an organic binder, a water-soluble binder and alcohol, subjected to wet-pulverization by a ball mill and dried to yield a pulverized powder material.
  • the pulverized powder material was compacted into a disc shape with a diameter of 19 mm and a thickness of 1.4 mm by uniaxial molding at about 30 MPa and cold isostatic pressing (CIP) at about 150 MPa.
  • the compact was sintered in the air at 1100°C or 1300°C for 2 to 4 hours.
  • a pair of electrodes was formed on the sintered compact by grinding opposite surfaces of the sintered compact, applying a silver paste to the ground opposite surfaces of the sintered compact and baking the silver paste.
  • the piezoceramic material was then completed by polarizing the sintered compact through the application of a direct-current voltage of 3 to 5 kV/mm between the electrodes in a silicone oil at 100 to 150°C.
  • each of the piezoceramic materials was tested for capacitance change rate ⁇ Cp, Curie temperature Tc, piezoelectric constant d33 and piezoelectric constant deterioration rate ⁇ d33 under the following conditions.
  • the evaluation test results are indicated in TABLE 1. Further, pictures of the piezoceramic materials were optionally taken by a scanning electron microscope. The electron microscopic picture of Comparative Example 5 is indicated in FIG. 1 .
  • the capacitance Cp(20) of the piezoceramic material at 20°C and the capacitance Cp(150) of the piezoceramic material at 150°C were measured ausing an impedance analyzer ("HP4194 type" available from Hewlett-Packard Company).
  • the Curie temperature Tc of the piezoceramic material was measured using an impedance analyzer ("HP4194A type” available from Hewlett-Packard Company) and an electric furnace.
  • the piezoelectric constant d33 of the piezoceramic material was measured by the resonance/anti-resonance method according to EMAS-6100 using a d33 meter (available from "Chinese Academy of Sciences") in combination.
  • the initial piezoelectric constant d33 of the piezoceramic material was measured in the same way as above.
  • the piezoceramic material was then subjected to heat-resistance test for 10 hours at 250°C in the air. After the heat-resistance test, the piezoelectric constant d33 of the piezoceramic material was measured in the same way as above.
  • the piezoceramic materials of Examples 1 to 9 (where 1.000 ⁇ m ⁇ 1.075, 0.470 ⁇ x ⁇ 0.490, 0.020 ⁇ y ⁇ 0.040, 0 ⁇ n ⁇ 1.000 and 0 ⁇ z ⁇ 0.025) had a capacitance change rate ⁇ Cp of 2500 ppm/K or lower, a Curie temperature Tc of 340°C or higher, a piezoelectric constant d33 of 340 pC/N or larger and a piezoelectric constant deterioration rate ⁇ d33 of -10% or better and thus showed good piezoelectric and temperature characteristics.
  • the piezoceramic material of Comparative Example 1 (where 0.490 ⁇ x) had a piezoelectric constant d33 of lower than 340 pC/N and a piezoelectric constant deterioration rate ⁇ d33 of over -10% and showed much inferior piezoelectric characteristics.
  • the piezoceramic material of Comparative Example 5 (where m > 1.075) had a piezoelectric constant d33 of lower than 340 pC/N and showed much inferior piezoelectric characteristics as PbO appeared in streak form in the piezoceramic material as shown in white in FIG. 1 .
  • the piezoceramic material of Comparative Example 6 (where m ⁇ 1) also had a piezoelectric constant d33 of lower than 340 pC/N and showed much inferior piezoelectric characteristics.
  • the piezoceramic material attains good piezoelectric and temperature characteristics by controlling the composition of the piezoceramic material as represented by Pb m ⁇ Zr 1-x-y-z Ti x Sn y (Sb 1-n Nb n ) z ⁇ O 3 where 1.000 ⁇ m ⁇ 1.075, 0.470 ⁇ x ⁇ 0.490, 0.020 ⁇ y ⁇ 0.040, 0 ⁇ n ⁇ 1.000 and 0 ⁇ z ⁇ 0.025.
  • Piezoceramic materials were produced in the same way as in Example 1 of Experiment 1 except for varying the sintering temperatures of the piezoceramic materials. Each of the piezoceramic materials was tested for piezoelectric constant d33 in the same way as in Experiment 1. After removing the electrodes from the surfaces of the piezoceramic material, the surface of the piezoceramic material was observed by XRD to determine the crystallite size of the piezoceramic material according to the Scherrer equation. The evaluation test results are indicated in TABLE 2 and FIG. 2 . Further, pictures of the piezoceramic materials sintered at 1250°C and 1300°C were taken by a scanning electron microscope.
  • FIGS. 3 and 4 The electron microscopic pictures are indicated in FIGS. 3 and 4 , respectively.
  • Sintering temperature (°C) 1000 1050 1100 1150 1200 1250 1300 d33 (pC/N) 320 365 384 381 358 347 312 Grain size ( ⁇ m) 0.6 0.8 1.2 1.6 2.0 3.0 3.5 Crystallite size (nm) 26.2 30.0 32.1 34.3 38.4 39.0 41.4
  • the piezoceramic material had a piezoelectric constant d33 of 340 pC/N or larger and a crystallite size of 30 to 39 nm when the sintering temperature was in the range of 1050 to 1250°C.
  • the piezoceramic material had a piezoelectric constant d33 of lower than 340 pC/N and a crystallite size of less than 30 nm or over 39 nm.
  • the crystallites of the piezoceramic material suddenly grew to coarse grains when the sintering temperature reached 1300°C. It has been thus shown that it is desirable to control the crystallite size of the piezoceramic material to within 30 to 39 nm by adjusting the sintering temperature etc. in order to improve the piezoelectric characteristics of the piezoceramic material.
  • sample sensors Samples of the non-resonance knock sensor 10 (hereinafter just referred to as “sample sensors") were produced as shown in FIGS. 5 to 7 by using the same piezoceramic materials as that of Example 1 of Experiment 1 as the piezoelectric element 15.
  • the element electrode 15a was formed by chamfering upper edges of the sintered compact of the piezoceramic material, printing a silver paste to a top surface, other than the chamfered edge regions, of the sintered compact of the piezoceramic material and baking the silver paste.
  • the resin molded part 11 was made of polyamide resin.
  • the lead electrodes 14 and 16 were made of brass.
  • the insulating plates 13p and 13t and the insulation sleeve 13s were made of PET (polyethylene terephthalate).
  • the weighting member 17 was made of iron-based material for Sample No. 5 and made of brass for Sample Nos. 1 to 4 and 6 to 9. In each of Sample Nos. 1 to 9, the weight of the weighting member 17 was controlled to 10.0 g. Further, the whole of the top surface SB of the element electrode 15a faced the bottom surface SB of the weighting member 17 when the piezoelectric element 15 and the weighting member 17 were projected in a thickness direction of the piezoelectric element 15. The area S1 of the bottom surface SA of the weighting member 17 was controlled to 225.5 mm 2 .
  • the area S2 of the top surface SB of the element electrode 15a was varied to adjust the surface area ratio S2/S1 to different values.
  • Each of the sample sensors were tested for capacitance Cp(20) at 20°C in the same way as in Experiment 1. Further, the output of the sample sensor across the terminal portions 14a and 16a was measured through the application of a shock of 3G by a vibrator. The evaluation test results are indicated in TABLE 3 and FIG. 8 . TABLE 3 No.
  • the sample sensor had an output of over 75 mV and showed practically favorable sensitivity when the surface area ratio S2/S1 was higher than or equal to 45%. It has been thus shown that it is desirable to control the surface area ratio S2/S1 to 45% or higher in order to secure high sensitivity in balance with cost performance.

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Claims (6)

  1. Matériau de céramique piézoélectrique dont la composition est représentée par :
    Pbm {Zr1-x-y-z Tix Sny (Sb1-n Nbn)z} O3
    où 1,000 ≤ m ≤ 1,075, 0,470 ≤ x < 0,490, 0,020 ≤ y ≤ 0,040, 0 < n < 1,000 et 0 < z ≤ 0,025 et présentant une taille de cristallite de 30 à 39 nm.
  2. Matériau de céramique piézoélectrique selon la revendication 1, dans lequel le matériau de céramique piézoélectrique présente une constante piézoélectrique d33 de 340 pC/N ou plus.
  3. Matériau de céramique piézoélectrique dont la composition est représentée par :
    Pbm {Zr1-x-y-z Tix Sny (Sb1-n Nbn)z}O3
    où 1,000 ≤ m ≤ 1,075, 0,470 ≤ x < 0,490, 0,020 ≤ y ≤ 0,040, 0 < n < 1,000 et 0 < z ≤ 0,025 et présentant une constante piézoélectrique d33 de 340 pC/N ou plus.
  4. Élément piézoélectrique (15) comprenant un corps élémentaire (15c) formé d'un matériau de céramique piézoélectrique conforme à l'une quelconque des revendications 1 à 3.
  5. Capteur piézoélectrique (10) comprenant :
    un élément piézoélectrique (15) comprenant un corps élémentaire (15c) formé d'un matériau de céramique piézoélectrique conforme à l'une quelconque des revendications 1 à 3 et d'au moins une paire d'électrodes (15a, 15b) agencée sur le corps élémentaire (15c),
    un élément formant support (12) comportant une partie formant support (12b) afin de porter l'élément piézoélectrique (15),
    un élément de poids (17) disposé sur l'élément piézoélectrique (15) afin de presser l'élément piézoélectrique (15) contre la partie formant support (12b), et
    une pièce moulée en résine (20) recouvrant l'élément piézoélectrique (15) et l'élément de poids (17) depuis l'état antérieur de l'élément formant support (12).
  6. Capteur piézoélectrique (10) comprenant :
    un élément piézoélectrique (15) comprenant un corps élémentaire (15c) formé d'un matériau de céramique piézoélectrique conforme à l'une quelconque des revendications 1 à 3 et d'une paire de première et seconde électrodes (15a, 15b) agencées sur le corps élémentaire (15c),
    un élément formant support (12) comportant une partie formant support (12b) afin de porter l'élément piézoélectrique est (15),
    un élément de poids (17) disposé sur l'élément piézoélectrique (15) afin de presser l'élément piézoélectrique (15) contre la partie formant support (12b),
    dans lequel au moins une partie de la surface (SB) de la première électrode (15a) fait face à la surface inférieure (SA) de l'élément de poids (17) lorsque l'élément piézoélectrique (15) et l'élément de poids (17) sont projetés dans la direction de l'épaisseur de l'élément piézoélectrique (15), et le rapport de la surface (S2) de ladite au moins une partie de la surface (SB) de la première électrode (15a) sur la surface (S1) de la surface inférieure (SA) de l'élément de poids (17) est de 45 % ou plus.
EP09003122.0A 2008-03-05 2009-03-04 Matériau piézocéramique, élément piézoélectrique et détecteur de cliquetis sans résonance Active EP2099082B1 (fr)

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